EP0701535A1 - METHOD FOR SYNTHESIS OF HIGH CAPACITY LixMn2O4 SECONDARY BATTERY ELECTRODE COMPOUNDS - Google Patents
METHOD FOR SYNTHESIS OF HIGH CAPACITY LixMn2O4 SECONDARY BATTERY ELECTRODE COMPOUNDSInfo
- Publication number
- EP0701535A1 EP0701535A1 EP94915439A EP94915439A EP0701535A1 EP 0701535 A1 EP0701535 A1 EP 0701535A1 EP 94915439 A EP94915439 A EP 94915439A EP 94915439 A EP94915439 A EP 94915439A EP 0701535 A1 EP0701535 A1 EP 0701535A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- compounds
- electrode
- compound
- intercalation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention relates to secondary, rechargeable lithium and lithium ion batteries, and more particularly relates to the synthesis of Li x Mn 2 0 4 intercalation compounds adapted for use as battery electrodes which provide extended high capacity.
- Li x Mn 2 0 4 intercalation compounds have shown exceptional promise as electrode materials in secondary batteries for all manner of portable electrical power needs. Such materials have been used with outstanding success in positive electrodes for batteries comprising lithium metal, as well as in positive lithium source intercalation electrodes for lithium ion batteries comprising, for example, intercalatable carbon electrodes .
- Li x Mn 2 0 4 electrode compounds have for some time generally been synthesized in a simple endothermic reaction between stoichiometric quantities of a lithium salt and a manganese oxide.
- Common precursors are, for example, the Li 2 C0 3 and MnO ⁇ compounds discussed by Hunter in U.S. Pat. 4,246,253.
- the spinel in which the lithium content, x, nominally approximates 1 is shown by Hunter to be readily obtained by heating a 2:1 mole ratio mixture of Mn.Li at 800-900°C for a time to ensure thorough reaction, and then cooling to ambient working temperature, usually room temperature.
- electrode materials of high, stable charge capacity may be prepared by heating a Li- and Mn-source compound mixture in air to a temperature in excess of about 800°C for a time sufficient to ensure optimum crystallization and cooling the resulting compound to at least about 500°C at a controlled rate of less than about 10 ⁇ C/hr before further cooling to ambient working temperature.
- This unique process apparently remedies the instabilities in the compound which are created at the initial high processing temperature and which result in the limited charging capacity of the ultimate electrodes .
- Such instabilities may be due to the likely existence of conditions at temperatures in excess of 800°C which lead to a substantial reduction of some manganese ions to the Mn ++ state in which they later exhibit a significant solubility in an organic battery cell electrolyte.
- the common practice of relatively rapid, uncontrolled cooling of synthesized LiMn 2 0 4 apparently maintains the reduced manganese ions in their lower valence state, whereas the controlled slow cooling step of the present invention provides sufficient reaction time at the lower temperature for these ions to reoxidize to their preferred Mn +4 or Mn +3 state.
- FIG. 1 presents graph traces showing comparative a-axis parameters of various rapidly- and slowly-cooled Li x Mn 2 0 4 compounds
- FIG. 2 presents graph traces showing comparative weight loss of rapidly- and slowly-cooled samples of a Li x Mn_0 compound
- FIG. 3 is a cyclic voltammogram of a secondary battery cell comprising Li/Li x Mn 2 0 electrodes showing a typical variation in current with applied voltage;
- FIG. 4 shows a representative battery cell, in cross- section, utilizing an electrode comprising a Li x Mn 0 4 intercalation compound prepared according to the present invention
- FIG. 5 is a portion of a voltammogram of FIG. 1 presented at increased scale to show the predominant 4.5V intercalation peak indicative of rapid cooling during synthesis of Li x Mn 0 4 ;
- FIG. 6 is a portion of a voltammogram of FIG. 1 presented at increased scale to show the predominant 4.9V intercalation peak indicative of controlled slow cooling during synthesis of
- FIG. 7 presents a series of graph traces showing the comparative variations of charge capacity over extended charging cycles for cells comprising rapidly-cooled Li v Mn 2 0 4 and slowly-cooled Li x Mn 2 0 4 of the present invention.
- FIG. 8 presents a series of graph traces showing the comparative variations of charge capacity over extended charging cycles for cells comprising slowly-cooled Li-.-Mn 2 0 ⁇ of the present invention having different levels, x, of lithium content.
- the cubic a-axis parameter of slowly-cooled samples e.g., those cooled from about an 800°C annealing temperature at less than about 10°C/hr, was significantly smaller, seldom exceeding about 8.23 A in nominal formulations with x greater than about 1.0.
- Li x Mn 2 0 4 compounds varying in the proportion of lithium, x were prepared both according to prior practices and according to the current innovative method. These procedures were essentially identical with the exception of the operation of cooling the compounds after the synthesis annealing. Stoichiometric proportions of Li C0 3 (other lithium compounds, such as LiOH, Lil, or Li 2 N0 3 might similarly be employed) and Mn0 2 (or another manganese source, such as its acetate or hydroxide compound) were thoroughly mixed and heated in air at ' about 800°C for about 72 hours.
- Li C0 3 other lithium compounds, such as LiOH, Lil, or Li 2 N0 3 might similarly be employed
- Mn0 2 or another manganese source, such as its acetate or hydroxide compound
- the other series of similar x range was "slowly" cooled at a rate of less than about 10 ' - ' C/hr, preferably at about 2-3°C/hr, to a temperature of about 500 ⁇ C before the annealing furnace was turned off and the samples allowed to rapidly cool to room temperature. The samples were then completed by grinding to a fine powder.
- Each of the samples was used to form a positive cell electrode in the normal manner by mixing the powdered Li x Mn 2 0 4 compound with about 5% carbon black and 5% polyvinylidene fluoride in 2-methyl phthalate, coating the resulting slurry onto an aluminum substrate, and heating for a time at about 200 ⁇ C.
- Swagelock test cells as represented in FIG. 4, were assembled using lithium metal foil as the negative electrode 42, an electrolyte separator layer 43 prepared of a IM solution of LiPF 6 in a 33:67 mixture of dimethylcarbonate and ethylene carbonate, and a positive sample electrode 44. Electrically conductive contacts 46 and leads 48 completed each cell.
- the cells were then tested over repeated C/3 charging cycles (one complete charge/discharge in 3 hours) using a potentiostatic mode coulometer (CRNS, Grenoble, France, Model “Mac-Pile", version A-3. Ole/881) .
- the voltage was varied from the open circuit level (about 3.4V) to the 5.1V limit of the instrument and then to about 4.25V for subsequent repeated cycling between 4.25 and 5.1V to obtain cyclovoltammetry traces, such as those shown in enlarged scale in FIGs . 5 and 6, in the range of the high-end intercalation peaks at 4.5 and 4.9V.
- the cycling voltage ranges were varied for other test series, as noted below.
- FIG. 7 charts variations in charging capacity, normalized as milliamp hours per gram of intercalation compound to account for differences in actual electrode weights.
- Traces 72 and 74 show the more stable maintenance of capacity in a preferred slow-cooled material, e.g., the Li 1 _ 05 Mn 2 O 4 compound of the previous FIGs., over respective 3-4.7V and 3-4.5V C/3 charging cycles.
- the rapid cooling of prior processes resulted in electrode materials which exhibited an immediate loss of about 30% of initial capacity over the first 50 cycles as shown by traces 76 and 78 for the respective 3-4.7V and 3- 4.5V C/3 charging cycles.
- the extended 3-4.5V C/3 cycling tests also revealed a significant variation in the capacity and stability of cells as a function of the initial amount of lithium in the intercalation compounds synthesized by the slow-cooling method of the invention.
- This effect of the variation of x in the Li Mn 2 0 4 compounds is shown in FIG. 8 where trace 82 indicates an optimum formulation where x is about 1.05.
- Traces 84 and 86 show effects of varying x to about 1.10 and 1.00, respectively, within which range the spinel is in a single phase.
- the effect of a deficiency of lithium on initial and extended cell capacity is shown in trace 88 where x is about 0.90.
- a series of lithium-ion battery cells was constructed from the Li x Mn 2 0 compounds prepared according to this invention.
- the previous lithium foil electrode 42 was replaced by a carbon electrode fashioned of a paste of powdered petroleum coke in a polyvinylidene binder solution coated and dried on a copper foil substrate.
- Graphite may likewise be used as an alternative form of carbon.
- the carbon serves as the negative electrode and intercalates, during the charging cycle, the Li-ions derived from the Li x Mn 2 0 4 positive electrode.
- Tests of repeated charge cycling showed cell capacities comparable to those previously described for the lithium cells using Li x Mn 2 0 4 spinels synthesized with slow cooling from annealing temperatures in excess of about 800°C. After extended recharging over as many as 4000 cycles, a representative cell was disassembled and the electrodes were examined.
- the positive electrode Li x Mn 2 0 4 continued to exhibit well-defined crystallinity under X-ray diffraction study.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/064,247 US5425932A (en) | 1993-05-19 | 1993-05-19 | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
US64247 | 1993-05-19 | ||
PCT/US1994/004776 WO1994026666A1 (en) | 1993-05-19 | 1994-04-28 | METHOD FOR SYNTHESIS OF HIGH CAPACITY LixMn2O4 SECONDARY BATTERY ELECTRODE COMPOUNDS |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0701535A1 true EP0701535A1 (en) | 1996-03-20 |
EP0701535A4 EP0701535A4 (en) | 1996-04-17 |
EP0701535B1 EP0701535B1 (en) | 1998-12-02 |
Family
ID=22054597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94915439A Expired - Lifetime EP0701535B1 (en) | 1993-05-19 | 1994-04-28 | METHOD FOR SYNTHESIS OF HIGH CAPACITY LixMn2O4 SECONDARY BATTERY ELECTRODE COMPOUNDS |
Country Status (8)
Country | Link |
---|---|
US (1) | US5425932A (en) |
EP (1) | EP0701535B1 (en) |
JP (1) | JP3164583B2 (en) |
CA (1) | CA2163087C (en) |
DE (1) | DE69415011T2 (en) |
DK (1) | DK0701535T3 (en) |
ES (1) | ES2127392T3 (en) |
WO (1) | WO1994026666A1 (en) |
Families Citing this family (71)
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US5820790A (en) * | 1994-11-11 | 1998-10-13 | Japan Storage Battery Co., Ltd. | Positive electrode for non-aqueous cell |
US5807646A (en) * | 1995-02-23 | 1998-09-15 | Tosoh Corporation | Spinel type lithium-mangenese oxide material, process for preparing the same and use thereof |
US5693307A (en) * | 1995-06-07 | 1997-12-02 | Duracell, Inc. | Process for making a lithiated lithium manganese oxide spinel |
US5693435A (en) * | 1995-08-16 | 1997-12-02 | Bell Communications Research, Inc. | Lix CoO2 electrode for high-capacity cycle-stable secondary lithium battery |
EP0762521B1 (en) * | 1995-09-06 | 1999-03-10 | Fuji Photo Film Co., Ltd. | Lithium ion secondary battery |
CA2158242C (en) * | 1995-09-13 | 2000-08-15 | Qiming Zhong | High voltage insertion compounds for lithium batteries |
US5874058A (en) * | 1995-10-06 | 1999-02-23 | Kerr-Mcgee Chemical Llc | Method of preparing Li1+x MN2-x O4 for use as secondary battery electrode |
US5601796A (en) * | 1995-11-22 | 1997-02-11 | The Board Of Regents Of The University Of Oklahoma | Method of making spinel LI2MN204 compound |
US5792442A (en) * | 1995-12-05 | 1998-08-11 | Fmc Corporation | Highly homogeneous spinel Li1+X Mn2-X O4 intercalation compounds and method for preparing same |
AU2606897A (en) * | 1996-04-05 | 1997-10-29 | Fmc Corporation | Method for preparing spinel li1+xmn2-xo4+y intercalation compounds |
US5976489A (en) * | 1996-04-10 | 1999-11-02 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
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US6337157B1 (en) * | 1997-05-28 | 2002-01-08 | Showa Denki Kabushiki Kaisha | Cathode electroactive material, production method and nonaqueous secondary battery comprising the same |
US6117410A (en) * | 1997-05-29 | 2000-09-12 | Showa Denko Kabushiki Kaisha | Process for producing lithiated manganese oxides by a quenching method |
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KR100378005B1 (en) * | 1997-06-30 | 2003-06-12 | 삼성에스디아이 주식회사 | Cathode active material for lithium ion battery having high capacity and stability, and method for producing the same |
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US6759167B2 (en) | 2001-11-19 | 2004-07-06 | The Gillette Company | Primary lithium electrochemical cell |
US7045252B2 (en) * | 2002-08-08 | 2006-05-16 | The Gillette Company | Alkaline battery including lambda-manganese dioxide |
JP5194835B2 (en) * | 2008-01-24 | 2013-05-08 | 株式会社豊田中央研究所 | Lithium manganese composite oxide, lithium ion secondary battery, and method for producing lithium manganese composite oxide |
US8142933B2 (en) * | 2009-09-30 | 2012-03-27 | Conocophillips Company | Anode material for high power lithium ion batteries |
US20110223477A1 (en) * | 2010-03-12 | 2011-09-15 | Nelson Jennifer A | Alkaline battery including lambda-manganese dioxide and method of making thereof |
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US8303840B2 (en) * | 2010-03-12 | 2012-11-06 | The Gillette Company | Acid-treated manganese dioxide and methods of making thereof |
US20110219607A1 (en) | 2010-03-12 | 2011-09-15 | Nanjundaswamy Kirakodu S | Cathode active materials and method of making thereof |
US9570741B2 (en) | 2012-03-21 | 2017-02-14 | Duracell U.S. Operations, Inc. | Metal-doped nickel oxide active materials |
US8703336B2 (en) | 2012-03-21 | 2014-04-22 | The Gillette Company | Metal-doped nickel oxide active materials |
US9028564B2 (en) | 2012-03-21 | 2015-05-12 | The Gillette Company | Methods of making metal-doped nickel oxide active materials |
EP2784853B1 (en) | 2013-03-27 | 2018-07-25 | Karlsruher Institut für Technologie | Lithium transistion metal titanate with a spinel structure, method for its manufacturing, its use, Li-ion cell and battery |
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1993
- 1993-05-19 US US08/064,247 patent/US5425932A/en not_active Expired - Fee Related
-
1994
- 1994-04-28 WO PCT/US1994/004776 patent/WO1994026666A1/en active IP Right Grant
- 1994-04-28 JP JP52549394A patent/JP3164583B2/en not_active Expired - Fee Related
- 1994-04-28 DE DE69415011T patent/DE69415011T2/en not_active Expired - Fee Related
- 1994-04-28 ES ES94915439T patent/ES2127392T3/en not_active Expired - Lifetime
- 1994-04-28 DK DK94915439T patent/DK0701535T3/en active
- 1994-04-28 EP EP94915439A patent/EP0701535B1/en not_active Expired - Lifetime
- 1994-04-28 CA CA002163087A patent/CA2163087C/en not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
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No further relevant documents disclosed * |
See also references of WO9426666A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1994026666A1 (en) | 1994-11-24 |
US5425932A (en) | 1995-06-20 |
CA2163087C (en) | 1999-06-08 |
JPH08509098A (en) | 1996-09-24 |
EP0701535A4 (en) | 1996-04-17 |
EP0701535B1 (en) | 1998-12-02 |
CA2163087A1 (en) | 1994-11-24 |
JP3164583B2 (en) | 2001-05-08 |
ES2127392T3 (en) | 1999-04-16 |
DE69415011T2 (en) | 1999-08-12 |
DE69415011D1 (en) | 1999-01-14 |
DK0701535T3 (en) | 1999-08-30 |
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